Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
  • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
  • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D241/20—Nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
  • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
  • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D241/26—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with nitrogen atoms directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
  • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
  • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
  • C07D241/40—Benzopyrazines
  • C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring

Definitions

• insects The control of insects is of vital importance in the increasingly populous world of today. It is well-known that insects such as the orders of Lepidoptera, Coleoptera, Diptera, Homoptera, Hemiptera and Orthoptera, at the larval stage, cause extensive damage to many crops, for example, food crops and fibrous crops. Control of such insects contributes to the well-being of civilization by increasing the supplies of food and of the fibrous materials useful in the production of clothing.
• This invention is directed to novel 1-(substituted benzoyl)-3-(substituted pyrazinyl)ureas having insecticidal activity, and to methods of use of the novel compounds.
• This invention relates to novel 1-(substituted benzoyl)-3-(substituted pyrazinyl)ureas of the formula ##STR1## wherein
• a and B are the same or different, and are halo, methyl, or trifluoromethyl;
• R 1 when taken separately, is hydrogen, halo, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, halo(C 1 -C 4 )alkyl, nitro, cyano, ##STR2## or naphthyl;
• R 2 when taken separately, is hydrogen, halo, methyl, ethyl, cyano, or halo(C 1 -C 2 )alkyl;
• R 1 and R 2 may not both be hydrogen at the same time
• R 3 is halo, halo(C 1 -C 4 )alkyl, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl, nitro, cyano, or phenyl;
• n 0, 1, 2, or 3;
• n 0 or 1
• X is --O--, --S--, or ##STR3##
• R 5 and R 6 are the same or different, and are hydrogen, halo, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, nitro, cyano, or halo(C 1 -C 4 )alkyl;
• R 7 and R 8 when taken separately, are the same or different, and are hydrogen, C 1 -C 4 alkanoyl, or C 1 -C 3 alkoxycarbonyl;
• a and B are the same or different, and are halo, methyl, or trifluoromethyl;
• R 1 when taken separately, is hydrogen, halo, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, halo(C 1 -C 4 )alkyl, nitro, cyano, ##STR7## or naphthyl;
• R 2 when taken separately, is hydrogen, halo, methyl, ethyl, cyano, or halo(C 1 -C 2 )alkyl;
• R 1 and R 2 may not both be hydrogen at the same time
• R 3 is halo, C 1 -C 6 alkyl, halo(C 1 -C 4 )alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl, nitro, cyano, or phenyl;
• n 0, 1, 2, or 3;
• n 0 or 1
• X is --O--, --S--, or ##STR8##
• R 7 and R 8 when taken separately, are the same or different, and are hydrogen, C 1 -C 4 alkanoyl, or C 1 -C 3 alkoxycarbonyl;
• a and B are the same and are halo or methyl
• R 1 when taken separately, is hydrogen, halo, C 1 -C 6 alkyl, cyano, ##STR11##
• R 2 when taken separately, is hydrogen, halo, methyl, ethyl, or cyano;
• R 1 and R 2 may not both be hydrogen at the same time
• R 3 is halo, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, or halo(C 1 -C 4 )alkyl;
• n 0, 1, or 2;
• n 0 or 1
• X is --O--
• R 5 and R 6 are the same or different, and are hydrogen, halo, or halo(C 1 -C 4 )alkyl;
• R 7 and R 8 are both hydrogen.
• a and B are the same, and are halo;
• R 1 is bromo, chloro, or ##STR13##
• R 2 is hydrogen, methyl, or ethyl
• R 3 is halo, C 1 -C 6 alkyl, or halo(C 1 -C 4 )alkyl;
• n 0, 1, or 2;
• R 7 and R 8 are hydrogen.
• halo refers to fluoro, chloro, and bromo.
• C 1 -C 6 Alkyl represents straight- or branched-chain saturated alkyl including methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, t-butyl, isobutyl, n-amyl, isoamyl, sec.-amyl, t-amyl, n-hexyl, isohexyl, t-hexyl and the like.
• Cycloalkyl represents saturated cycloalkyl having from 3 to 6 carbon atoms in the ring and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
• Halo(C 1 -C 4 )alkyl represents trifluoromethyl, 1,1-difluoroethyl, pentafluoroethyl, 1,1,2,2-tetrafluoroethyl, chlorodifluoromethyl, trichloromethyl, 2-bromoethyl, 3-bromopropyl, 4-bromobutyl, 3-chloropropyl, 3-chlorobutyl and the like.
• C 2 -C 4 Alkanoyl refers to acetyl, propionyl and butyryl.
• C 1 -C 3 Alkoxycarbonyl refers to methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and isopropoxycarbonyl.
• Halo(C 1 -C 2 )alkyl refers to trifluoromethyl, 1,1-difluoroethyl, pentafluoroethyl, 1,1,2,2-tetrafluoroethyl, chlorodifluoromethyl, trichloromethyl, 2-bromoethyl, and the like.
• C 1 -C 4 Alkoxy represents methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec.-butoxy, and t-butoxy.
• C 1 -C 4 Alkylthio represents methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec.-butylthio, and t-butylthio.
• C 1 -C 4 Alkylsulfonyl represents methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and the like.
• Novel compounds coming within the scope of the generic formula above include, but are not limited to the following:
• novel compounds of this invention have been found to be active as insecticides by their action in interfering with the growth of sensitive insects.
• the compounds appear to interfere with the molting process of the insects and thus cause death.
• the compounds have been found to act on the insects as a result of the insects ingesting the compounds, e.g., by ingesting the leaves and foliage treated with the active compounds, or ingesting any other part of their normal habitat, e.g., water, manure, and the like, to which the active compounds have been applied. Because of this property, the compounds are useful in a novel method of controlling insects at the larval stage.
• novel compounds of this invention are prepared by procedures known to the art.
• novel compounds are prepared by allowing a 2,6-disubstituted-benzoylisocyanate to react with an aminopyrazine or an aminoquinoxaline, to yield the desired 1-(2,6-disubstituted benzoyl)-3-(substituted 2-pyrazinyl)urea.
• 2,6-disubstituted-benzoylisocyanates are readily prepared from, for instance, 2,6-disubstitutedbenzamides, following the general procedure of Speziale et al., J. Org. Chem. 27, 3742 (1962).
• 2-amino-5-chloropyrazine is prepared following the general procedure of Palamidessi and Bernardi, J. Org. Chem. 29, 2491 (1964), wherein methyl 2-amino-3-pyrazinylcarboxylate is allowed to react with chlorine in acetic acid to yield methyl 2-amino-5-chloro-3-pyrazinylcarboxylate.
• This ester is hydrolyzed with aqueous sodium hydroxide to yield 2-amino-3-carboxy-5-chloropyrazine, which is then heated in tetrahydronaphthalene and decarboxylated to yield the desired 2-amino-5-chloropyrazine.
• 2-amino-5,6-dichloropyrazine is prepared by allowing 2-amino-6-chloropyrazine to react with N-chlorosuccinimide in chloroform to yield a mixture of 2-amino-5,6-dichloropyrazine, 2-amino-3,6-dichloropyrazine, and 2-amino-3,5,6-trichloropyrazine. The mixture is then separated by column chromatography and the desired 2-amino-5,6-dichloropyrazine is obtained.
• 2-amino-5(or 6)-substituted pyrazines useful in preparing the novel final compounds of this invention are prepared utilizing oxime derivatives of certain ketones.
• 2-oxopropanal 1-oxime and 2-oxobutanal 1-oxime are prepared from ethyl acetoacetate and ethyl propioacetate, respectively, following the procedure of Meyer et al., Chem. Ber. 11, 695 (1878).
• Other oxime intermediates are prepared from such ketones as acetophenone, 2,4-dimethylacetophenone, p-chloroacetophenone, and benzyl methyl ketone, following the general procedure of Claisen et al., Chem. Ber.
• ketones such as p-methoxypropiophenone, p-bromobutyrophenone, p-bromopropiophenone, and methyl neopentyl ketone, following the general procedure of Hartung et al., J. Am. Chem. Soc. 51, 2262 (1929).
• Yet another oxime intermediate is prepared from t-butyl methyl ketone, which is first transformed into t-butylglyoxal using the procedure of Fuson et al., J. Am. Chem. Soc. 61, 1938 (1939).
• the t-butylglyoxal in aqueous solution at pH 4-5, is allowed to react with acetone oxime (commercially available) at about room temperature for about two days.
• the reaction product mixture is worked up by extracting it with ether, and the t-butylglyoxal oxime is isolated from the ether extract as colorless needles having a melting point of about 50°-52° C.
• the intermediate 2-amino-5-methylpyrazine is prepared stepwise, starting with 2-oxopropanal 1-oxime.
• This oxime is allowed to react with aminomalononitrile tosylate [prepared by the method of Ferris et al., J. Am. Chem. Soc. 88, 3829 (1966)], to yield 2-amino-3-cyano-5-methylpyrazine 1-oxide.
• the pyrazine 1-oxide prepared in this manner is allowed to react with phosphorous trichloride to yield 2-amino-3-cyano-5-methylpyrazine.
• This 2-amino-3-cyano-5-methylpyrazine is hydrolyzed with aqueous sodium hydroxide to yield 2-amino-3-carboxy-5-methylpyrazine, which, when heated in tetrahydronaphthalene, is decarboxylated to yield the desired 2-amino-5-methylpyrazine.
• Another intermediate pyrazine compound, 2-amino-5-(4-bromophenyl)-6-methylpyrazine is synthesized starting with 1-(4-bromophenyl)-1,2-propanedione 2-oxime, which oxime is obtained by the same general procedure of Hartung et al., supra.
• This oxime is allowed to react with aminomalononitrile tosylate, and the product, the substituted pyrazine 1-oxide, is allowed to react with phosphorus trichloride in tetrahydrofuran, according to the procedure of Taylor et al., J. Org. Chem.
• 2-amino-5,6-dimethylpyrazine is prepared from 2-chloro-5,6-dimethylpyrazine, which in turn is prepared according to the procedure of Karmas et al., J. Am. Chem. Soc. 74, 1580-1584 (1952).
• Still other pyrazine intermediate compounds can be prepared starting with 2,5-dichloropyrazine, which itself can be prepared by the procedure of Palamidessi and Bernardi, J. Org. Chem. 29, 2491 (1964).
• This 2,5-dichloropyrazine can be used as the starting material for the phenoxy, phenylthio, or phenylsulfonyl substituted pyrazine intermediates, or the corresponding substituted phenoxy, phenylthio, or phenylsulfonyl substituted pyrazine intermediates.
• 2,5-dichloropyrazine can be allowed to react with an equivalent of phenoxide or thiophenoxide ion in a suitable solvent such as ethanol, t-butanol, dimethylformamide, acetonitrile, or the like, at a temperature in the range of from about 0° to about 120° C., to yield the corresponding 2-chloro-5-phenoxy(or phenylthio)pyrazine.
• a suitable solvent such as ethanol, t-butanol, dimethylformamide, acetonitrile, or the like
• the 2-chloro-5-phenoxy(or phenylthio)pyrazine can be converted to the corresponding 2-amino-5-phenoxy(or phenylthio)pyrazine by reaction with ammonium hydroxide at a temperature in the range of about 150°-200° C. in a high pressure reaction vessel for a time sufficient to give substantially complete conversion.
• the 2-amino-5-phenoxy(or phenylthio)pyrazine obtained in this manner can then be used to prepare the 1-(substituted benzoyl)-3-[5-phenoxy(or phenylthio)-2-pyrazinyl]ureas.
• Homologous phenoxy or phenylthio compounds can be prepared in the same general manner.
• the 2-chloro-5-phenylthiopyrazine intermediate, or homolog thereof, can be oxidized to the 2-chloro-5-phenylsulfonylpyrazine intermediate through the use of such oxidizing agents as peracetic acid or m-chloroperbenzoic acid.
• Suitable solvents for use in carrying out this reaction include acetic acid, chloroform, methylene chloride, and the like.
• Suitable reaction temperatures for the oxidation can range from about 20° to about 70° C.
• the 2-chloro-5-phenylsulfonylpyrazine can then be allowed to react with ammonia or ammonium hydroxide in a high pressure reaction vessel, at a temperature of about 100° to about 200° C. to yield the 2-amino-5-phenylsulfonylpyrazine intermediate. Reaction conditions may vary depending on the chemical structure of the phenylsulfonyl grouping.
• 2-aminoquinoxalines which are simply aminobenzopyrazines, are also prepared by methods well known in the art.
• 2-aminoquinoxaline is prepared by allowing the commercially available 2-chloroquinoxaline to react with ammonia in a suitable solvent such as ethanol at the temperature of a steam bath.
• o-phenylenediamines which are not commercially available are readily prepared from the corresponding dinitroanilines by hydrogenation.
• the hydrogenations are carried out by using anhydrous hydrazine in the presence of 5% ruthenium on carbon (Engelhard Industries) in a suitable solvent, such as commercial absolute ethanol, at a temperature of about 55°-70° C.
• 5% ruthenium on carbon Engelhard Industries
• 5-cyano-3-nitro-o-phenylenediamine is readily prepared by the selective hydrogenation of 4-cyano-3,5-dinitroaniline in the presence of 5% ruthenium on carbon in ethanol as solvent, together with anhydrous hydrazine.
• 3-nitro-5-trifluoromethyl-o-phenylenediamine is prepared from 2,6-dinitro-4-trifluoromethylaniline.
• o-phenylenediamines useful in preparing the quinoxaline intermediates for synthesizing the novel compounds of this invention are prepared by reduction of commercially available o-nitroanilines through the use of 5% palladium on carbon catalyst in a low pressure hydrogenation apparatus. For example, 2-nitro-4-trifluoromethylaniline is reduced in this manner to yield 4-trifluoromethyl-o-phenylenediamine.
• the 2-amino-6-chloroquinoxaline and 2-amino-7-chloroquinoxaline are prepared by methods well known in the art, and elegantly described in The Chemistry of Heterocyclic Compounds, Condensed Pyridazine and Pyrazine Rings, Part III, Quinoxalines, Chapter XXIV et seq., page 203 et seq., by J. C. E. Simpson, [Arnold Weissberger, Consulting Editor, Interscience Publishers, Inc., New York (1953)].
• 3,4-diaminochlorobenzene is allowed to react with glyoxylic acid to yield a mixture of 6-chloro-2-hydroxyquinoxaline and 7-chloro-2-hydroxyquinoxaline.
• the mixture in turn is allowed to react with phosphorous oxychloride to yield a mixture of 2,6-dichloroquinoxaline and 2,7-dichloroquinoxaline.
• the mixture is allowed to react with anhydrous ammonia in a suitable solvent, dimethylsulfoxide being the solvent of choice, to yield a mixture of 2-amino-6-chloroquinoxaline and 2-amino-7-chloroquinoxaline.
• novel compounds of this invention are prepared by allowing the 2-aminopyrazine or 2-aminoquinoxaline intermediate compounds to react with a 2,6-disubstituted-benzoylisocyanate to yield the corresponding 1-(substituted benzoyl)-3-(substituted pyrazinyl)urea.
• the preparation is exemplified as follows: 2,6-dichlorobenzoylisocyanate is allowed to react with 2-amino-5-chloropyrazine in cold ethyl acetate. The reaction mixture is stirred overnight at room temperature.
• the product is isolated by evaporating the ethyl acetate solvent and adding a mixture of ether and hexane to the residue. A solid is precipitated which is then purified by recrystallization from a suitable solvent such as ethanol. There is obtained a product having a melting point of about 201°-204° C., which product is identified by elemental analyses and NMR and infrared spectra as 1-(5-chloro-2-pyrazinyl)-3-(2,6-dichlorobenzoyl)-urea.
• a 1-(substituted benzoyl)-3-(substituted pyrazinyl)urea is allowed to react under suitable conditions with, for example, a dihalodimethyl ether, or with oxalyl chloride, to yield a 3-(substituted pyrazinyl)-5-(substituted benzoyl)-2,3,5,6-tetrahydro-1,3,5-oxadiazin-4-one, or a 1-(substituted benzoyl)-3-(substituted pyrazinyl) parabanic acid, respectively.
• This compound was prepared stepwise. The first step followed the procedure of Dallacker et al., Ann. 660, 98-103 (1962).
• Compound 1 having a melting point of about 132°-135° C., was identified as 2-amino-3,6-dichloropyrazine.
• Compound 2 having a melting point of about 132°-134° C., was identified as 2-amino-3,5,6-trichloropyrazine.
• Compound 3 having a melting point of about 143°-144° C., was identified as 2-amino-5,6-dichloropyrazine, the desired compound.
• This intermediate was prepared stepwise.
• This intermediate was prepared from 2-chloro-5,6-dimethylpyrazine, which chloro compound was prepared according to the procedure of Karmas et al., J. Am. Chem. Soc. 74, 1580-1584 (1952).
• This intermediate pyrazine was prepared via a stepwise procedure.
• This intermediate pyrazine was prepared via a stepwise procedure.
• the carboxypyrazine (prepared above), about 500 mg., was refluxed in 5 ml. of tetrahydronapthalene for about 2 hours.
• the reaction product mixture was cooled and hexane added thereto.
• the solid which precipitated was filtered off. It weighed about 470 mg., and was identified by NMR and IR spectra as 2-amino-5-phenyl-6-methylpyrazine.
• the pyrazine 1-oxide obtained above was then allowed to react with phosphorus trichloride to yield 2-amino-3-cyano-5-t-butylpyrazine, which was in turn hydrolyzed and decarboxylated to yield 2-amino-5-(t-butyl)pyrazine, identified by IR spectrum.
• the starting oxime material for this pyrazine intermediate was prepared according to the procedure of Hartung et al., J. Am. Chem. Soc. 51, 2262 (1929), from methyl neopentyl ketone, and identified by IR and NMR spectra as neopentylglyoxal oxime.
• This intermediate pyrazine was prepared stepwise.
• This intermediate was prepared via a stepwise procedure.
• the hot solution was filtered through a pad of filter aid (Hyflo-Super Cel, a diatomaceous earth, Johns-Manville Products Corp.) which was then washed with hot ethanol.
• the combined filtrates were concentrated under vacuum and chilled.
• the solid which precipitated was filtered off, washed with cold ethanol and dried, to give 657 g. of crude product.
• the crude product was recrystallized from 2 liters of methanol by the addition of 2 liters of water and chilling to give 600 g. (68% yield) of red solid, having a melting point of about 125° C.
• the product was identified as 3-nitro-5-trifluoromethyl-o-phenylenediamine.
• This intermediate compound was also prepared stepwise.
• This 7-trifluoromethylquinoxalin-2-one was allowed to react with phosphorus oxychloride (in the same manner as described above for 6-trifluoromethylquinoxalin-2-one) to yield the intermediate 2-chloro-7-trifluoromethylquinoxaline having a melting point of about 119°-120° C.
• This compound was allowed to react with ammonia, in the manner described above, to yield the 2-amino-7-trifluoromethylquinoxaline, having a melting point of about 192°-194° C., and identified by IR spectrum.
• the compounds of the present invention are useful for the control of insects of various orders, including Coleoptera such as Mexican bean beetle, boll weevil, corn rootworm, cereal leaf beetle, flea beetles, borers, Colorado potato beetle, grain beetles, alfalfa weevil, carpet beetle, confused flour beetle, powder post beetle, wireworms, rice weevil, rose beetle, plum curculio, white grubs; Diptera, such as house fly, yellow fever mosquito, stable fly, horn fly, blowfly, cabbage maggot, carrot rust fly; Lepidoptera, such as Southern armyworm, codling moth, cutworm, clothes moth, Indianmeal moth, leaf rollers, corn earworm, European corn borer, cabbage worm, cabbage looper, cotton bollworm, bagworm, eastern tent caterpillar, sod webworm, fall armyworm; and Orthoptera, such as German cockroach and American cockroach.
• novel compounds of the invention interfere with the mechanism of metamorphosis which occurs in insects, causing the death of the insects.
• novel compounds of this invention are formulated for use as insecticides by being mixed with a solid carrier material or dissolved or dispersed in a liquid carrier material. Included in such mixtures, if desired, are adjuvants such as surface-active substances and stabilizers.
• formulations can include aqueous solutions and dispersions, oil solutions and oil dispersions, pastes, dusts, wettable powders, miscible oils, granules, aerosol preparations and the like.
• the wettable powders, pastes and miscible oils are formulations in concentrated form which are diluted with water before or during use.
• the granular preparations are produced by taking up the novel compound in a solvent, after which granular carrier material such as porous granules, for example, pumice or attapulgite clay, mineral non-porous granules, such as sand or ground marl, and organic granules are impregnated with the solution, suitably in the presence of a binder.
• granular carrier material such as porous granules, for example, pumice or attapulgite clay, mineral non-porous granules, such as sand or ground marl, and organic granules are impregnated with the solution, suitably in the presence of a binder.
• Such preparations contain about 1 to about 15 percent active ingredient, suitably about 5 percent.
• Dust formulations are prepared by intimately mixing the active compound with an inert solid carrier material in a concentration of for example from about 1 to about 50 percent by weight.
• suitable solid carrier materials include talc, kaolin, diatomaceous earth, dolomite, gypsum, chalk, bentonite, attapulgite or mixtures of these and similar substances. It is also possible to use organic carrier materials such as ground walnut shells or the like.
• Wettable powder formulations are produced by mixing from about 10 to about 80 parts by weight of a solid inert carrier, such as one of the aforementioned carrier materials, with from about 10 to about 80 parts by weight of the active compound, together with from about 1 to about 5 parts by weight of a dispersing agent, such as for example, the ligninsulfonates or alkylnaphthalenesulfonates, and preferably also with from about 0.5 to about 5 parts by weight of a wetting agent, such as one of the fatty alcohol sulfates, alkylarylsulfonates, or fatty acid condensation products.
• a dispersing agent such as for example, the ligninsulfonates or alkylnaphthalenesulfonates
• a wetting agent such as one of the fatty alcohol sulfates, alkylarylsulfonates, or fatty acid condensation products.
• Miscible oil formulations are prepared by dissolving the active compound in or suspending the active compound in a suitable solvent which is preferably rather immiscible with water, after which an emulsifier is added to the preparation.
• suitable solvents include xylene, toluene, high aromatic petroleum distillates, for example solvent naphtha, distilled tar oil, and mixtures of these.
• Suitable emulsifiers include alkylphenoxypolyglycol ethers, polyoxyethylene sorbitan esters of fatty acids, or polyoxyethylene sorbitol esters of fatty acids. These miscible oils contain the active compound in a concentration of about 2 percent to about 50 percent by weight.
• aerosol preparation can be obtained in the usual manner by incorporating the active compound in a solvent in a volatile liquid suitable for use as a propellant, for example, one of the commercially available fluorocarbon propellant.
• the preparations containing one of the active compounds of this invention may also include other known pesticidal compounds. This of course broadens the spectrum of activity of the preparation.
• the amount of 1-(substituted benzoyl)-3-(substituted pyrazinyl)urea to be applied for insect control purposes to a given area of plant life is, of course, dependent upon a variety of factors, such as the extent of vegetative surface to be covered, the severity of the insect infestation, the condition of the foliage treated, the temperature, the humidity, etc. In general, however, the application of sufficient formulation to result in an application rate of the active ingredient of about 0.1 to about 1000 ppm. is desirable.
• the insecticidal activity of the novel compounds of this invention has been determined by testing the efficacy of formulations of the compounds against Mexican bean beetle larvae (Epilachna varivestia), and against Southern armyworm larvae (Spodoptera eridania) in an insecticide screen. These insects are members of the Coleoptera and Lepidoptera orders of insects, respectively. The compounds have been tested in several tests against these insects at rates of from about 1000 ppm. down to about 1 ppm, the compounds being applied at these rates to leaves of plants upon which the above-identified larvae feed.
• Bean plants were grown in four-inch square pots with there being 6 to 10 plants per pot. When the plants were 10 days old, they were ready for use in this experiment.
• test compound was formulated by dissolving 10 mg. of the test compound in 1 ml. of solvent (23 g. Toximul R plus 13 g. Toximul S per liter of 1:1 anhydrous ethanol and acetone) followed by mixing with 9 ml. of water to give a 1000 parts per million concentration of the test compound in the solution.
• solvent 23 g. Toximul R plus 13 g. Toximul S per liter of 1:1 anhydrous ethanol and acetone
• This solution of test compound was then sprayed onto the 4-inch square pots of bean plants containing 6 to 10 plants per pot. The plants were allowed to dry and then 12 leaves were removed and the cut ends wrapped in water-soaked cellucotton.
• the leaves were divided between six 100 ⁇ 20 mm. plastic petri dishes. Five second-instar Mexican bean beetle larvae (Epilachna varivestis) and five second- and third-instar Southern armyworm larvae (Spodoptera eridania) were placed in each of three dishes. The dishes were then placed in a room wherein the temperature and relative humidity were controlled at about 78° F. and about 51 percent, respectively, for a period of about four days, at which time the first evaluation of the effects of the test compounds was made. After this evaluation, two fresh leaves from the original treated pots were placed in each dish. The dishes were again maintained in the temperature and humidity controlled room for an additional three days until the final seven day evaluation was made.
• the percent control was determined by counting the number of living larvae per dish. All the treatments were compared to solvent controls and nontreated controls.
• the rating code (percent of control) used was as follows:
• Table 1 The results of this test are set forth in Table 1, which follows.
• column 1 identifies the compounds by the number of the preparative example; and columns 2 through 5 give the Rating Code at days 4 and 7 for the two insects against which the compounds were tested at the application rate of 1000 ppm.
• test compound Ten mg. of test compound was dissolved in 1 ml. of solvent and mixed with 9 ml. of water to give a 1000 ppm solution.
• the solvent used was 50:50 alcohol:acetone plus 23 g. of Toximul R and 13 g. of Toximul S per liter.
• Each test compound was formulated by dissolving 4 mg. of the compounds in 0.4 ml. of acetone and mixing with 40 g. of homogenized beef liver to give a 100 ppm. mixture.
• the liver was prepared by trimming off excess fat and connective tissue and homogenizing the liver in a blender.
• Each of these cups was infested with 20, 2-day-old blowfly larvae. The infested liver was covered with more ab-sorb-dri, and the cups were capped with a perforated lid. All the cups, treated and control, were maintained in a room under controlled conditions of temperature and humidity (as described in Experiment 1) until the control larvae pupated. All the pupae were removed and placed in 100 ⁇ 200 mm. plastic petri dishes and held until adult flies emerged.
• the number of pupae per cup was recorded at the time the pupae were placed in the petri dishes.
• the number of emerged adults per dish was recorded and the percent adult control was calculated in the same manner and according to the same formula as used in Experiment 3.
• test results are recorded in Table 4, which follows.
• column 1 identifies the test compounds; columns 2 to 5 give the percent adult control accomplished at the indicated application rates.
• test compound was formulated by dissolving 10 mg. of the compound in 1 ml. of acetone and mixing with 99 ml. of water to give a concentration of 100 ppm of the compound in the test solution. The lower concentrations of test solutions needed were then obtained by serial dilution of the 100 ppm solution with water. These test solutions were then placed in 100 ml. glass beakers, or, alternatively, 6 oz. plastic containers, 40 ml. of test solution per beaker or container, and 2 beakers or containers per rate. Twenty to thirty, 24-hour mosquito larvae were placed in each beaker. The larvae were fed 10-20 mg. of pulverized Purina laboratory chow daily for 7 days. During this time the beakers or containers were maintained in a room in which the temperature and humidity were continuously controlled and recorded, as described in Experiment 1.
• the percent mortalities of the mosquito larvae were determined after 7 days by visual observation of the number of living larvae. All the treatments were compared to solvent and nontreated controls. The results are set forth in Table 5, which follows.
• column 1 identifies the compounds by the number of the preparative example; column 2, the application rate in ppm; and column 3, the percent mortality at the indicated test rates.

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• Chemical & Material Sciences (AREA)
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• Plural Heterocyclic Compounds (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

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• 1975
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• 1976
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• 1978
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